CN103819594B - A kind of polyolefin plastics optically and biologically degrading property-modifying additive and preparation thereof and application - Google Patents
A kind of polyolefin plastics optically and biologically degrading property-modifying additive and preparation thereof and application Download PDFInfo
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Abstract
The present invention provides a kind of polyolefin plastics optically and biologically degrading property-modifying additive, it is characterised in that be structured with formula:The present invention also proposes the preparation method and application of a kind of polyolefin plastics optically and biologically degrading property-modifying additive。Due to the particular design of structure, the controllable optic biological degradation polyolefine additive that the present invention proposes can and polyolefin substrate between there is good affinity, it is simple to it is homogeneously dispersed in polyolefin substrate；Itself there is good light-biological activity, the optically and biologically degrading performance of polyolefin substrate and the induction period of regulation and control degraded can be improved again。The controlled optically and biologically degrading additive that the present invention proposes, by controlling its adding proportion in polyolefin substrate, can control polyolefin plastics degradable in 1.5-30 month, have high using value。
Description
Technical field
The present invention relates to polymer arts, in particular it relates to a kind of controllable optic biological degradation polyolefine additive and its preparation method and application, and comprise the compositions of this controllable optic biological degradation polyolefine additive。
Background technology
Polyolefin includes the materials such as polyethylene, polypropylene or polystyrene, is presently the most a conventional important general-purpose plastics of class。Owing to having easy-formation, proportion is little, mechanical property good, the advantage such as reusable and nontoxic, thus polyolefin plastics is widely used in the fields such as automobile, household electrical appliances, article of everyday use and disposable film packing material。In daily life, polyolefin plastic products use in whole plastic accounts for increasing proportion, including non-returnable container materials such as substantial amounts of packaging bag, household electrical appliance foam vibration-absorptive material and packing boxes。
Polyolefinic use brings very big convenience to our production and life, but also brings some problems。Due to features such as the easily aging of plastics and crackies, its life cycle is very short, and substantial amounts of plastic particularly packing material just goes out of use after about 6～12 months, and the plastics of 40% were converted into waste plastics after 1～2 year。Owing to the polyolefin of high molecular is difficult to by daylight and microbial degradation, environment, by long-term existence out of doors, is caused " white pollution " by polyolefin garbage。Currently, most wasted polyolefine is by burning or landfill disposal, but burning disposal can produce a large amount of toxic gas；And fill and relate to land seizure and the problem cannot degraded for a long time。This problem at home and abroad obtains most attention, is always up the focus of plastics industry research about the research of Degradable polyolefin and production。
The biodegradable plastic being synthetically derived can solve the problem of environmental pollution of plastics, but the current price of such biodegradable plastic is higher, it is difficult to promotes。Compared with general-purpose plastics, particularly in the thin-gage goods such as thin film, the mechanical property of biodegradable plastic and hot property are often difficult to reach instructions for use, it is difficult to practical, also cannot substitute conventional plastic。
Starch filled filled-type degradation plastic such as grade belongs to half degradative plastics；Owing to only making implant degrade, can not there is obvious degraded in polymer itself, and the plastics of a large amount of fragmentations further increase the difficulty of recycling, make pollution more serious。And the addition of biodegradable implant often reduces the physical property of plastics so that it is difficult quality adapts to the demand in market。
The factors such as mixed economy, ecology and instructions for use, taking to add photodegradable aid, to prepare the method for controlled photodegradable polymers/plastics more practical, feasible。Some existing patent application or documents, as: US Patent No. 5854304(publication date: on December 29th, 1998), and Chinese patent CN1174856A(application number: 96109080.4, publication date: on March 4th, 1998) etc. adopt carboxylate or the complex adding the transition metal such as ferric diethyl dithiocarbamate, cerium stearate, ferric stearate, ferrocene, manganese stearate, ferric acetyl acetonade, cobaltous octadecanate, zinc stearate or calcium stearate method, it is possible to accelerate polyolefinic light degradation。But, belong to micromolecular carboxylate or complex due to these additives, if doping is easily caused the mechanical properties decrease of plastics more at most；There is bigger difference with polyolefin in the character being additionally, since micromolecule additive, even if making masterbatch with polyolefin in advance, also easily causes its skewness in the plastic。When this manufactured goods carry out light degradation, it is easy to the local decomposition rate causing additive concentration high is too fast or the time is too short, have impact on the useful life of plastics；And concentration is low or does not have the local degradation speed of additive cross slowly or do not degrade, have impact on the degradation property of plastics。
In the information of some patent application publication, outside in addition to this light degradation auxiliary agent of transition metal organic salt, also add natural multicomponent organic acid (citric acid or fumaric acid etc.) and make oxidation-biological degradation polyalcohol/plastics, overcome the problem that later stage biodegradation produced by single light degradation is slower, but still suffer from the problems such as light degradation skewness described above。
Summary of the invention
In order to overcome above-mentioned technical problem, an object of the present invention is in that, it is provided that a kind of polyolefin plastics optically and biologically degrading property-modifying additive。
Another object of the present invention is to, it is provided that the preparation method of a kind of polyolefin plastics optically and biologically degrading property-modifying additive。
3rd purpose of the present invention is to propose the application of described polyolefin plastics optically and biologically degrading property-modifying additive。
The technical scheme realizing above-mentioned purpose of the present invention is:
A kind of polyolefin plastics optically and biologically degrading property-modifying additive, is structured with formula:
Wherein, n is the number of repeat unit of parent's matrix segment, n=150～2000。M is the number of repeat unit with light degradation function segment, m=10～50；
Wherein, R is the one in H, methyl, chlorine or phenyl；Preferably, R is H, methyl or phenyl。
M is ferrum, cerium, manganese, cobalt, nickel, zinc or calcium。
Wherein, the molecular weight of described parent's base polyolefin segment is 3000～50000；The molecular weight of the described construction unit with optically and biologically degrading function is 300～5000。
In the present invention, there is the existence of optically and biologically degrading functional group, it is possible to make polyolefin generation optically and biologically degrading, improve polyolefinic optically and biologically degrading performance；The existence of parent's base polyolefin segment can improve and the polyolefinic compatibility, homogeneous polymer can be formed with polyolefin, prevent described controllable optic biological degradation polyolefine additive skewness or loss in polyolefin, thus improving polyolefinic optically and biologically degrading performance。
A kind of preparation method of polyolefin plastics optically and biologically degrading property-modifying additive, it includes step:
Hydroxide reactant salt by oxidized polyolefin or organic acid graft-modified polyolefin and transition metal, according to making reactant contains the ratio that weight/mass percentage composition is 0.1～10% of transition metal, add the hydroxide salt of transition metal, at 120-140 DEG C, react 2-5h, obtain controllable optic biological degradation polyolefine additive；
Described Oxidized polyolefin hydrocarbon structure is as follows:
Wherein, the hydroxide salt of described transition metal is: cobalt hydroxide, cerium hydroxide, nickel hydroxide, zinc hydroxide, calcium hydroxide or manganous hydroxide。
Preferably, described hydroxide salt is to add with the form of its methanol solution。
Wherein, described oxidized polyolefin can select commercially available prod, it is preferred to use following preparation method: being melted by polyolefin or be dissolved in organic solvent, adding oxidizing, oxidizing reaction temperature is 110-200 DEG C, oxidation time 10-20h, obtains oxidized polyolefin；Described organic solvent is toluene or dimethylbenzene。
It is further preferred that the preparation method of described oxidized polyolefin is:
Polyolefin melted or is dissolved in organic solvent, passing into the gas containing oxygen, at 135-195 DEG C, carry out oxidation reaction, when the acid number of reactant mixture is 5～100mgKOH/g, preferably when the acid number of reactant mixture is 20-40mgKOH/g, stopped reaction, obtain oxidized polyolefin。
The described gas containing oxygen, it is possible to be air, it is also possible to be the gas of 0-100 part air and 10 parts of oxygen mix。
Wherein, described organic acid graft-modified polyolefin can select commercially available prod, it is preferred to use following preparation method:
Polyolefin melted or is dissolved in organic solvent, adding the organic acid of polyolefin quality 1-10% and the peroxide of polyolefin quality 0.01-0.1%, at 110-200 DEG C, carry out graft reaction, response time 4-8h, obtain the improved polyalkene of organic acid grafting；
Described organic acid is maleic acid, fumaric acid, acrylic acid, methacrylic acid, one or more in itaconic acid；Described peroxide is the one in hydrogen peroxide, acetyl peroxidating sulphonyl hexamethylene, tertbutanol peroxide, benzoyl peroxide, peracetic acid, benzylhydroperoxide；Described organic solvent is toluene or dimethylbenzene。
In preparation method, it is preferable that according to making reactant contains the ratio that weight/mass percentage composition is 0.5-5% of transition metal, add the hydroxide salt of transition metal, at 120-140 DEG C, react 2.5-3.5h。
The organic solvent adopted in preparation reaction is that this area common are machine solvent, it is preferred to toluene or dimethylbenzene。
The polyolefin plastics optically and biologically degrading property-modifying additive that the present invention proposes application in preparing polyolefin plastics。During application, described controllable optic biological degradation polyolefine additive is directly mixed with polyolefin substrate。
It is possible to further described controllable optic biological degradation polyolefine additive is mixed with polyolefin substrate by the mode of solution blending or melt blending。
Wherein, the mass ratio that described polyolefin plastics optically and biologically degrading property-modifying additive adds in polyolefin substrate is 0.1%～10%, it is preferred to 0.5%～5%；Described polyolefin substrate includes polyethylene, polypropylene, polystyrene, polyethylene/polypropylene copolymers, polybutadiene or one or more in polrvinyl chloride。
Preferably, described polyolefin substrate is also added with accounting for macromolecule antioxidant and/or the free radical absorbent of polyolefin plastics optically and biologically degrading property-modifying additive 5-30%, it is preferable that accounting example 5-10%。
Wherein, described macromolecule antioxidant is phenolic resin, phenols macromolecule antioxidant, high molecular phosphite ester kind antioxidant, one in sulfur-bearing macromolecule antioxidant, for instance irgasfos 168, antioxidant 1010, antioxidant 264, antioxidant 1076, antioxidant 2246-S etc.。
Wherein, described free radical absorbent is 2,2-diphenyl-1-trinitrophenyl-hydrazine, 1,4-benzoquinone, 2,6-ditertbutylparacresol, tetramethyl-benzoquinone, 2-methyl-2-nitromethane, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, and the one in phenyl-N-tert-butylnitrone。
The compositions comprising described controllable optic biological degradation polyolefine additive provided by the invention, including following components: described controllable optic biological degradation polyolefine additive, and macromolecule antioxidant or free radical absorbent。Described macromolecule antioxidant/free radical absorbent controllable degraded induction period, to be adapted to the different user demands of polyolefin substrate。
In application, by described controllable optic biological degradation polyolefine additive and macromolecule antioxidant or free radical absorbent, and polyolefin substrate mixes。
It is possible to further by the mode of solution blending or melt blending by described controllable optic biological degradation polyolefine additive and macromolecule antioxidant or free radical absorbent, and polyolefin substrate mixing。
The beneficial effects of the present invention is:
The present invention develops a kind of controlled optically and biologically degrading additive novel, for polyolefin substrate, and this new additive agent is totally different from existing additive/polymer, and addition is little；Polyolefin is evenly distributed, does not affect polyolefinic mechanics and hot property, and degradation time is controlled, fundamentally solve " white pollution " problem of China。
Due to the particular design of structure, the controllable optic biological degradation polyolefine additive that the present invention proposes can and polyolefin substrate between there is good affinity, it is simple to it is homogeneously dispersed in polyolefin substrate；Itself there is good light-biological activity, the optically and biologically degrading performance of polyolefin substrate and the induction period of regulation and control degraded can be improved again。
The controlled optically and biologically degrading additive that the present invention proposes, by controlling its adding proportion in polyolefin substrate, can control polyolefin plastics degradable in 1.5-30 month, have high using value。
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of embodiment 1 oxidic polyethylene。
Fig. 2 is the ultraviolet degradation curve of embodiment 1 polyethylene。
Fig. 3 is the induction period regulation and control curve of embodiment 1 Different adding amount polyethylene degradation。
Fig. 4 is the polyacrylic ultraviolet degradation curve of embodiment 2。
Fig. 5 is the ultraviolet degradation curve of embodiment 4 polystyrene。
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention。
NM technological means in the present invention, for the technological means that this area is conventional。
The material used in the present invention, for the conventional material that can commercially obtain。
In the present invention, in the described controllable optic biological degradation polyolefine additive prepared, the amount of the transition metal contained is weight/mass percentage composition。
Embodiment 1
Weigh 100g polyethylene and put into reactor, start stirring, pass into air, heat up gradually, after reaching 140 DEG C, every 30 minutes sampling and measuring acid numbers and molecular weight；When acid number increases to 5mg (KOH)/more than g, reducing reaction temperature to 130 DEG C, continue reaction 16h, prepared acid number is the oxidic polyethylene of 30mg (KOH)/g, and its structural formula is:
Structure verification data are shown in Fig. 1。
Above-mentioned 100g oxidic polyethylene adds the heating of 100mL dimethylbenzene melt, by the carboxyl of oxidic polyethylene with cobalt molar equivalent than the methanol solution (volume (or quality) concentration of cobalt hydroxide is 5%) for 2:1 addition cobalt hydroxide, react 3h in 130 DEG C；Solvent is removed in decompression, and preparation is 1.4%(weight/mass percentage composition containing cobalt) modified oxidized polyethylene (i.e. the controllable biologically degraded polyethylene additive containing cobalt), its structural formula is:
The close base polyolefin segment of above-mentioned additive is polyethylene, and repetitive is 420, and molecular weight is 12000g/mol；The segment with optically and biologically degrading function is the segment containing cobalt, and number of repeat unit is 20, and molecular weight is 2000。
The controllable biologically degraded polyethylene additive 1.2g containing cobalt obtained and macromolecule antioxidant 0.08g or free radical absorbent 0.1g is mixed and made into polyethylene optically and biologically degrading compositions；Macromolecule antioxidant is phenols macromolecule antioxidant 264, and free radical absorbent is 2,2-diphenyl-1-trinitrophenyl-hydrazines, obtains polyethylene optically and biologically degrading compositions。
Joining in polyvinyl resin by above-mentioned polyethylene optically and biologically degrading compositions, the addition of compositions is the 1% of polyvinyl resin quality, it is possible to the degradation time controlling polyvinyl resin is 18 months (referring to Fig. 2)。Owing to polyethylene optically and biologically degrading compositions has close matrix polyethylene segment, compositions can easily and uniformly be dispersed in polyethylene；And owing to additive addition is little, there is again close basal body structure, so affecting seldom on the physical property such as mechanical property, heat resistance of polyethylene base material, the physical property of controllable biologically degraded polyethylene is close with polyethylene。Referring to Fig. 3, can regulate and control the induction period of polyethylene degradation by adjusting the addition of optically and biologically degrading additive, in Fig. 3, curve 1 is the polyvinyl resin adding compositions 0.7%, degraded induction period 12 months, curve 2 is the polyvinyl resin adding compositions 1.2%, degraded induction period 24 months。
Embodiment 2
Weigh 100g polypropylene and put into reactor, start stirring, pass into air, heat up gradually, after reaching 140 DEG C, sampling and measuring acid number and molecular weight at regular intervals。When acid number increases to 5mg (KOH)/more than g, reducing reaction temperature to 130 DEG C, continue reaction 16h, prepared acid number is its chlorinated polypropylene of 38mg (KOH)/g。
Above-mentioned 100g its chlorinated polypropylene adds the heating of a small amount of dimethylbenzene melt, by the carboxyl of its chlorinated polypropylene with cerium molar equivalent than the methanol solution for 4:1 addition cerium hydroxide, react 3h in 130 DEG C。Solvent is removed in decompression, and preparation is containing the modified oxidized polypropylene that cerium is 1.8%。
The controllable biologically degraded Polypropylene Additive 1.2g containing cerium obtained and macromolecule antioxidant 0.08g or free radical absorbent 0.1g is mixed and made into polyethylene optically and biologically degrading compositions；Macromolecule antioxidant is phenols macromolecule antioxidant 264, and free radical absorbent is 2,2-diphenyl-1-trinitrophenyl-hydrazines, obtains compositions。
Joining in acrylic resin by above-mentioned polypropylene optically and biologically degrading compositions, the addition of compositions is the 0.8% of acrylic resin quality, it is possible to the degradation time controlling acrylic resin is 22 months (Fig. 4)。
Embodiment 3
100g polyolefin, 8g maleic acid are dissolved in 100mL dimethylbenzene, and logical nitrogen protection, oil bath is warming up to 120 DEG C, was dividedly in some parts 0.08g benzoyl peroxide (adding 0.08g altogether) every 20 minutes, terminates after stirring reaction 5h。After being cooled to room temperature, pour, to product, the ethanol that about triploid is long-pending into, obtain white precipitate。Use buchner funnel sucking filtration, and with acetone soak overnight。Carry out secondary precipitation again followed by xylene soluble, repeated precipitation 2～3 times, to wash remaining maleic acid monomer off。Product be placed in baking oven 60 DEG C dry to constant weight, prepare maleic acid graft-modified polyolefin。
Above-mentioned 100g maleic acid graft polyolefin adds the heating of a small amount of dimethylbenzene melt, by the carboxyl of maleic acid graft polyolefin with nickel molar equivalent than the methanol solution for 2:1 addition nickel hydroxide, react 3h in 130 DEG C。Decompression remove solvent, prepare nickeliferous be 5% graft-modified polyolefin。
The nickeliferous controllable biologically degraded maleic acid graft-modified polyolefin additive 1.2g obtained and macromolecule antioxidant 0.08g or free radical absorbent 0.1g is mixed and made into polyethylene optically and biologically degrading compositions；Macromolecule antioxidant is phenols macromolecule antioxidant 264, and free radical absorbent is 2,2-diphenyl-1-trinitrophenyl-hydrazines, obtains polyolefin optically and biologically degrading compositions。
Joining in vistanex by said polyolefins optically and biologically degrading compositions, the addition of compositions is the 1.3% of vistanex quality, it is possible to the degradation time controlling vistanex is 12 months。
Embodiment 4
Weigh 100g polystyrene and put into reactor, start stirring, pass into air, heat up gradually, after reaching 140 DEG C, sampling and measuring acid number and molecular weight at regular intervals。When acid number increases to 5mg (KOH)/more than g, reducing reaction temperature to 130 DEG C, continue reaction 16h, prepared acid number is the zinc oxide/poly styrene of 52mg (KOH)/g。
Above-mentioned 100g zinc oxide/poly styrene adds the heating of a small amount of dimethylbenzene melt, by the carboxyl of zinc oxide/poly styrene with manganese molar equivalent than the methanol solution for 2:1 addition manganous hydroxide, react 3h in 130 DEG C。Solvent is removed in decompression, and preparation is containing the modified oxidized polystyrene that manganese is 2.1%。
The polystyrene optically and biologically degrading specialist additive 1.2g of synthesis and macromolecule antioxidant 0.08g or free radical absorbent 0.1g is mixed and made into polystyrene optically and biologically degrading compositions；Macromolecule antioxidant is phenols macromolecule antioxidant 264, and free radical absorbent is 2,2-diphenyl-1-trinitrophenyl-hydrazines, obtains polystyrene optically and biologically degrading compositions。
Joining in polystyrene resin by above-mentioned polystyrene optically and biologically degrading compositions, the addition of compositions is the 1.8% of polystyrene resin quality, it is possible to the degradation time controlling polystyrene resin is 8 months (Fig. 5)。
Although, above the present invention is described in detail with a general description of the specific embodiments, but on basis of the present invention, it is possible to it is made some modifications or improvements, and this will be apparent to those skilled in the art。Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention。
Claims (11)
1. a polyolefin plastics optically and biologically degrading property-modifying additive, it is characterised in that be structured with formula:
Wherein, n is the number of repeat unit of parent's matrix segment, n=150～2000；M is the number of repeat unit with light degradation function segment, m=10～50；
Wherein, R is the one in H, methyl, chlorine or phenyl；
M is ferrum, cerium, manganese, cobalt, nickel, zinc or calcium。
2. polyolefin plastics optically and biologically degrading property-modifying additive according to claim 1, it is characterised in that R is H, methyl or phenyl。
3. the preparation method of a polyolefin plastics optically and biologically degrading property-modifying additive, it is characterised in that include step:
Hydroxide reactant salt by oxidized polyolefin or organic acid graft-modified polyolefin and transition metal, according to making reactant contains the ratio that weight/mass percentage composition is 0.1～10% of transition metal, add the hydroxide salt of transition metal, at 120-140 DEG C, react 2-5h, obtain polyolefin plastics optically and biologically degrading property-modifying additive；
Wherein, the hydroxide salt of described transition metal is: cobalt hydroxide, cerium hydroxide, nickel hydroxide, zinc hydroxide or manganous hydroxide；
Wherein, the preparation method of described oxidized polyolefin is: is melted by polyolefin or is dissolved in organic solvent, pass into the gas containing oxygen, oxidation reaction is carried out at 135-195 DEG C, oxidation time 10-20h, when the acid number of reactant mixture is 5～100mgKOH/g, stopped reaction, obtain oxidized polyolefin；Described organic solvent is toluene or dimethylbenzene。
4. preparation method according to claim 3, it is characterised in that when the acid number of reactant mixture is 20～40mgKOH/g, stopped reaction。
5. preparation method according to claim 3, it is characterised in that the preparation method of described organic acid graft-modified polyolefin is:
Polyolefin melted or is dissolved in organic solvent, adding the organic acid of polyolefin quality 1-10% and the peroxide of polyolefin quality 0.01-0.1%, at 110-200 DEG C, carry out graft reaction, response time 4-8h, obtain the improved polyalkene of organic acid grafting；
Described organic acid is maleic acid, fumaric acid, acrylic acid, methacrylic acid, one or more in itaconic acid；Described peroxide is the one in hydrogen peroxide, acetyl peroxidating sulphonyl hexamethylene, tertbutanol peroxide, benzoyl peroxide, peracetic acid, benzylhydroperoxide；Described organic solvent is toluene or dimethylbenzene。
6. preparation method according to claim 3, it is characterised in that according to making to contain in reactant the ratio that weight/mass percentage composition is 0.5-5% of transition metal, add the hydroxide salt of transition metal, reacts 2.5-3.5h at 120-140 DEG C。
7. the application in preparing polyolefin plastics of the polyolefin plastics optically and biologically degrading property-modifying additive described in claim 1 or 2。
8. application according to claim 7, it is characterized in that, the mass ratio that described polyolefin plastics optically and biologically degrading property-modifying additive adds in polyolefin substrate is 0.1%～10%, described polyolefin substrate includes polyethylene, polypropylene, polystyrene, ethylene/propene copolymer, polybutadiene or one or more in polrvinyl chloride。
9. application according to claim 8, it is characterised in that the mass ratio that described polyolefin plastics optically and biologically degrading property-modifying additive adds in polyolefin substrate is 0.5%～5%。
10. the application according to claim 7 or 8, it is characterised in that be also added with accounting for macromolecule antioxidant and/or the free radical absorbent of polyolefin plastics optically and biologically degrading property-modifying additive 5-30% in described polyolefin substrate；
Wherein, described macromolecule antioxidant is phenolic resin, phenols macromolecule antioxidant, high molecular phosphite ester kind antioxidant, the one in sulfur-bearing macromolecule antioxidant；
Wherein, described free radical absorbent is 2,2-diphenyl-1-trinitrophenyl-hydrazines, 1,4-benzoquinone, 2,6 ditertiary butyl p cresol, tetramethyl-benzoquinone, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, and the one in phenyl-N-tert-butylnitrone。
11. application according to claim 10, it is characterised in that be also added with accounting for macromolecule antioxidant and/or the free radical absorbent of polyolefin plastics optically and biologically degrading property-modifying additive 5-10% in described polyolefin substrate。
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